JPS60245632A - Improvement of fluidity of injection-moldable aromatic polyesters - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION It is known that fully aromatic esters are suitable for use in molding compositions. The synthesis of fully aromatic polyesters of the type to which the present invention is principally concerned is disclosed in US Pat.
No. 637,595, the disclosures of which are hereby included for reference. Another patent disclosing the molding properties of aromatic polyesters, particularly oxybenzoyl polyesters, is U.S. Pat. No. 3,662.

052.3,849,362 and 4,219°629
It is.

Other groups of aromatic polyesters that can be used include 2.6-
Aromatic polyesters containing repeating centers of dicarboxynaphthalene moieties and/or p-oxybenzoyl moieties and symmetric dioxyaryl moieties and variations thereof. Such polyesters are described in U.S. Patent No. 4.067.852.4,083,829.4.
゜130.545.4, 161.470.4, 184.
996.4, 219, 461.4, 224°433.4
, 238; 598.4, 238, 599.4. ．． 256
, 624.4, 265, 802.4.279, 803.
4,31.8,841 and 4.318,842.

The oxybenzoyl polyesters used in this invention can be used with a variety of fillers of types and amounts that promote or, at a minimum, do not substantially affect the desired properties. Examples of suitable fillers include, inter alia, glass fi/di-1 ground glass, polytetrafluoroethylene, pigments and talc, as well as the known common fillers and combinations thereof.

For the special use of molding compositions based on oxybenzoyl polyesters, a new oven pan that can be used in both thermal and microwave ovens is currently under application by the common assignee entitled "Plastic oven pan". No. 450,949, the disclosure of which is hereby incorporated by reference.

Another improvement in the manufacture of such baking pans using talc with special properties as a filler is disclosed in the currently pending application entitled "Improved Plastinum Baking Pans Containing Talc" by the common assignee. The question is Mf! i issue 4
No. 017659, and the disclosures thereof are also included here for reference.

Efforts continue to develop more effective molding compositions and improvements in molded T-culms.

It has been discovered in the present invention that fully aromatic polyesters, especially oxybenzoyl polyesters, can be endowed with good molding properties and good processability by adding small amounts of oxybenzoyl polyesters of a specific composition.

Although the present invention generally applies to all of the resins described in the above-identified currently pending application, it specifically applies to tribasic acid moieties, hydroxyaromatic acid moieties and aromatic diols containing about 1 : Suitable for resins derived from terephthalic acid, p-hydroxybenzoic acid and biphenol, respectively, present in a molar ratio of 2:1. Other molar ratios can also be used, and each molar ratio is 1:3:
1.1:5:1, l-near: 1, l-: 3, 5:1
and 1:l:l.

The flowability of all the resins mentioned in the previous section is improved by adding small amounts of resins in which the terephthalic acid reactant is completely or partially replaced by isophthalic acid. The resulting resins found to be effective as wave modifiers have the following units: where p=Q-Q, 9 and q=0.1-1.00;
r=1-7, s=0, 3-1.00, and t=Q-o, 7]. A preferred composition is a unit force (p=0,
It consists of polyester with q=l, 01r=1-5, and s=1.0.

It has also been discovered that when isophthalic acid is the dibasic acid reactant for producing the flow modifier, all or a portion of the biphenol reactant can be replaced by hydroquinone.

The proportion of p-hydroxybenzoic acid can be varied.

The flow modifier has a melting point greater than about 250°C;
and have no adverse effect on the thermal stability of the final resin formulation, nor do they alter the color or color stability in the final molded product.

They may be added to the substrate molding resin compound, e.g. from about 1% to about 2%.
It can be added in small amounts of 0% and preferably about 2 to about 10%.

The compositions of the present invention can be manufactured by extrusion according to generally known practices. For example, a two-screw extruder with an exhaust port having vacuum capability can be used with the addition of the polymer, selected talc, and titanium dioxide to the feed port.

The composition so produced can then be injection molded using techniques known in the injection molding art according to common practice.

The invention is further illustrated by the following examples, in which all parts and percentages are by weight unless otherwise indicated. These non-limiting examples are designed to teach those skilled in the art how to carry out the invention and to illustrate the best possible mode of carrying out the invention. This is an example.

The term MF (melt flowability), as used in unfiled applications, is defined in ASTM 01238 as the extrusion rate of a material, gllO
Defined as minutes. The test conditions for the compounds described in this application are to pass the material through an orifice 0.315 inches long and 0.0825 inches in diameter at 410° C. under a load of 38 pounds.

The term compression fluidity (CF) as used in this application is the flowability measurement of a gravimetric sample when compressed at 500 pounds on a Carver@press. It is measured from the area of a disk obtained from a sample of powdered material of a specified weight, generally 0.5-1.0 g, which is compressed between two parallel plates. To carry out this property measurement, the sample is compressed between two aluminum foil sheets backed by a 6"x6°'xi/4" chrome-plated steel plate. Copper 2112-X motel, l1 No. 15, modified for 800 and below.
A 0-C hydraulic press is used for compression of the sample. The specified temperature of the press is that indicated during the experiment for each sample.

The sample material is left between the plates under the specified pressure for 5 minutes to allow the temperature of the material to equilibrate with the press temperature. Next 5000
Apply a pound load for 2 minutes. Next, CF is calculated based on the following principles. The area of the compressed molding compound is 2
Measured by cutting an aluminum sand inch from a sample compressed between two sheets of aluminum foil. Aluminum foil has a known area/weight relationship called the foil modulus. The area is standardized with respect to the pressure of the applied load, and the number of
Multiply by 00 to give a number greater than l. The compression fluidity is then calculated by the following formula: 100% This example describes the synthesis of a copolyester used as a substrate molding resin in the present invention.

268 parts of biphenol, 396 parts of para-hydroxybenzoic acid, 693.40 parts of acetic anhydride and 238 parts of terephthalic acid were mixed and heated to a temperature of 315°C for 5 hours. The reaction mixture was stirred during the heating period. When a temperature of 315°C was reached, the polymer contents were removed from the reaction vessel and passed through a 20-2 American standard sieve series.
The particles were ground to a particle size in the 0.00 mensius range. The resin particles were gradually raised to a temperature of 354°C in an oven over a period of 16 hours and recovered as a granular powder.

On a two-screw extruder equipped with a vacuum (100-150 mmHg), 257.5 parts of the polymer of Example 1, 30 parts of rutile titanium dioxide, and 212.5 parts of natural talc were added. Plate-like structure, loss on ignition of 2% by weight, iron content of 0°5% analyzed as Fe2O3 and 95% of particles
Example 1 by extruding a mixture of high purity talcum with a particle size distribution such that the particle size distribution is greater than or equal to 40 microns.
A molding composition was produced from the polymer.

956 parts of biphenol, 1411 parts of halahydroxybenzoic acid, 2449 parts of acetic anhydride, 743 parts of terephthalic acid and 106 parts of isophthalic acid were mixed and 29
Heating was carried out to a temperature of 5°C for 5 hours at a rate of temperature increase of 30°C per hour. The reaction mixture was stirred during the heating period. 2
When a temperature of 95° C. is reached, the polymer contents are removed from the reaction vessel, cooled and sieved using a 20°C American standard sieve series.
The particles were ground to particle sizes in the -200 mm and 200 mm range. The resin particles were gradually raised to a temperature of 366°C in an oven over 11 hours and recovered as a granular powder with CF=58 at 404°C.

699 parts of biphenol, 1913 ffl of halahydroxybenzoic acid, 2573 parts of acetic anhydride and 620 parts of isophthalic acid were mixed and heated to a temperature of 304° C. for 5 hours at a rate of 30° C. per hour. did. The reaction mixture was stirred during the heating period. When a temperature of 300°C was reached, the melt was poured into a two-wooden mechanical mixer and mixed for 4 hours at 324°C. Upon cooling, the melt has a CF = 217 @ 270 °C and an intrinsic viscosity of 0.85 (■) (0 ° 1% in pentafluorophenol)
It became a solid with .

699 parts of biphenol, 1913 parts of parahydroxybenzoic acid, 2573 parts of acetic anhydride, 620 parts of isophthalic acid and 2.1 parts of Mg(OAc)2.4H20 were mixed and brought to a temperature of 255°C. 35 per hour for 3 hours
Heating was performed at a temperature increase rate of °C. The reaction mixture was stirred during the heating period and kept at 255-265°C for an additional hour. The melt was then poured into a two-arm mechanical mixer and mixed for 4 hours at 260°C. Upon cooling, the melt becomes CF=64@270°C and IV-1,0
It changed into a solid with .

The following examples illustrate the use of flow modifier resins to impart superior flow properties to the substrate oxybenzoyl polyester molding compound.

The copolymer of Example 3, CF=58, was prepared in powder form in Example 2.
Pelleft of the molding composition was mixed in a ratio of 5 parts of the resin of Example 3 to 95 parts of the composition of Example 2. The resulting mixture was molded in comparison to a control consisting of the unmodified composition of Example 2. Molding conditions and corresponding storage temperatures are shown below.

Area ↓ Area M Area work 〆Castle N Molding degree storage temperature control 355℃ 360℃ 350℃ 350℃ 23
0℃ 424℃ modified composition 355℃ 360℃ 35
0°C 350°C230°0 419°C storage temperature was reduced by 5°C with the additive, so that the modified composition showed better flowability.

'LLL1 50% of Reitaker, Clark & Gouniel r7) P o-lyt al 4545 talc and 50% of isophthalic acid according to Example 5 in a molar ratio of 1:3.71:1.00, p- A blend of resin made from hydroxybenzoic acid and biphenol was compounded on a medium-screw extruder and recovered as a pellet.

A formulation consisting of 4% of the resin thus produced and 96% of the pellet of the composition of Example 2 was prepared in Example 2.
and a control consisting of an unmodified composition. Molding conditions and corresponding storage temperatures are shown below.

1 ridge Koishio Tei Eiko is 5 moromi is for control 360°0365℃ 355℃ 355℃ 2
50'0 424℃ modified composition 360℃ 365℃
355°C 355°C 250'0 408°C The modified composition and molded parts, which are formulations molded with relatively low torque, have better gloss and lower viscosity during molding than the control ones. showed that. Storage temperature is 16°
Only C was lowered.

A flow modifier resin was prepared from isophthalic acid, parahydroxybenzoic acid and biphenol in a molar ratio of 1 to 3.71 to 1.005 according to the process of Example 3 of Photoform JA. 10%
This resin was blended with 42% Polyta 145, 45.8% rutile titanium dioxide and 40% of the resin of Example 2.

B, 50% of the resin of Example 1 to 42% of Polyt a
1 4545 and 8% rutile titanium difluoride to produce a molding composition.

A mixture of Compositions A and B above was compounded in the proportions shown in the table below and extruded into pellets in a 1 inch Killion extruder. The ease of extrusion and melt flow properties (MF) shown in the table below demonstrate the effectiveness of the flow modifier.

Soil W O Z Buried Ca C" 1 night property E8 Ampere p upper y lower IQOO8,3340 9645,6420,15 9374,4450,21 90103,2520,41 87132,8573,1 Amount of highly fluid material As the pressure (CF) and melt flowability (MF) of the extruded berene increases,
) both increased.

Examples 9 and 10 The following examples demonstrate flow modifiers for increasing filler levels that can be combined with a substrate oxybenzoyl molding resin without adversely affecting the properties of parts molded from highly filled molding resins. Explains the use of resin.

1300 copies of oven-dried Potters E-300
0 glass bulbs, 100 parts of rutile Ti, 70% filler content consisting of 2.560 parts of substrate oxybenzoyl polyester as described in Example 1 and 40 parts of flow modifier as described in Example 5. 620″ each
Extruded on a 1 inch Killion extruder with zones (feed) 1.2 and 3 set at F, 7206F' and 740'F. At 30RPM the ammeter reads 3-4
Only amps were recorded (empty extrusion draws about 1/2 amp). A light gray/beige fused ribbon (no gooey) was extruded under these conditions. The ribbon was cut and the resulting pieces were injection molded on a 30 ton Newbury machine.

A tray measuring 3 x 3 inches with a thickness of 73 mils was molded;
It has a tie tap impact strength of 0.74 ft-lbs and has improved scratch strength and swelling over trays made with molding compounds containing 42% or less spheres. It had resistance. Similar compositions using the same oxybenzoyl polyester resin, TiO2 and E-glass in compositions containing more than 50% filler without the flow modifiers described herein can be mixed ( extrusion) was not possible.

cy) 83 mm ”Z S K
” The following formulation was extruded using a 2-screw extruder at a speed of 300 bonds/hour 1 inch and 125 RPM.

Formulation I (50% level) - 50 parts of the resin described in Example 1, 45.5 parts of Polyta 14545 talc and 4.5 parts of rutile TiO2° Formulation II (60%
Level) - 38 parts of the resin described in Example 1, 2 parts of the flow modifier described in Example 5, 55 parts of Po
Iyt a 14545 talc and 5 parts rutile TiO
Formulation 1 containing more than 2.10% filler was also extruded at a significantly lower torque than the formulation containing no flow modifier.

The extruded pellets showed the following fluidity: Specific gravity Mixture 1 Yu Moekin Seven” (50%) (130%) Melt M fluidity @ 41O°C! (770 below) 0.27
0.52 These formulations were tested on a Windzuru 180 ton machine 1- ASTM test sample and 1o II X5 II
molded into a tray. Despite its relatively high loading, Formulation II was molded at a lower torque and at a measured storage temperature of 10°C lower than a formulation that did not contain flow modifiers. The resulting physical properties were completely acceptable.

The ratios used in the examples under 1-1 and in the claims are molar ratios.

Claims (1)

[Claims] 1. In a method for molding products containing aromatic oxybenzoyl polyesters, a small amount of the following units [wherein p=o-o, 9, q=0.1-1.00,
r=1-7, s=0, 3-1.00, and t=o-0,7]. 2. The ratio of units in the formula is P=O1 (1=1.0, r-1-
5, and s=1.0. 3. The method of claim 1, wherein the wave modifier is present in an amount of about 1% to about 20%. 4. The method of claim 1, wherein the wave modifier is present in an amount of about 2% to about 10%. 5. The method according to claim 1, wherein the aromatic oxybenzoyl polyester is a polyester produced by the reaction of terephthalic acid, p-hydroxybenzoic acid and biphenol. 6. The method according to claim 1, wherein the aromatic oxybenzoyl polyester is a polyester produced by the reaction of isophthalic acid, p-hydroxybenzoic acid and biphenol. 7. Aromatic oxybenzoyl polyester is produced by the reaction of a mixture of isophthalic acid and terephthalic acid, p~hydroxybenzoic acid and biphenol! 52. The method of claim t51, wherein the polyester is a polyester manufactured by II. 8. The method of claim 5, wherein terephthalic acid, p-hydroxybenzoic acid and biphenol are present in respective ratios of 1:0.1:1 to 1:15:L. 9. Terephthalic acid, p-hydroxybenzoic acid and biphenol are present in a ratio of 1:2:1. A method according to claim 5. 10, a small amount of the following units [where p=0-0.9, (1=0.1-1.0o-c'
, r-1-7, s=0.3-1.00, and t=O-0,7] and an aromatic oxybenzoyl Composition consisting of polyester. 11. The middle ratio in claim 8 is po, Q
9. The composition of claim 8, wherein r=1.0, r=1-7, and s=1.0. 12. The composition of claim 8, wherein the flow modifier is present in an amount of about 1% to about 20%. 13. The composition of claim 9, wherein the flow modifier is present in an amount of about 2% to about 10%. 14. The composition according to claim 8, wherein the aromatic oxybenzoyl polyester is a polyester produced by the reaction of terephthalic acid, p-hydroxybenzoic acid and biphenol. 15. The composition according to claim 8, wherein the aromatic oxybenzoyl polyester is a polyester produced by the reaction of isophthalic acid, p-hydroxybenzoic acid and biphenol. 16. The composition according to claim 8, wherein the aromatic oxybenzoyl polyester is a polyester produced by the reaction of a mixture of isophthalic acid and terephthalic acid, p-hydroxybenzoic acid and biphenol. 17. The composition of claim 12, wherein terephthalic acid, p-hydroxyammonium, folic acid and biphenol are present in a respective ratio of 1:0.1:1 to 1:15:1. . 18. The composition of claim 12, wherein terephthalic acid, p-hydroxybenzoic acid and biphenol are present in a ratio of 1:2:L.